Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS20040096582 A1
Publication typeApplication
Application numberUS 10/294,431
Publication dateMay 20, 2004
Filing dateNov 14, 2002
Priority dateNov 14, 2002
Also published asUS7531679, US7786320, US7910765, US8153833, US20090281344, US20100285663, US20110183528, US20120178267
Publication number10294431, 294431, US 2004/0096582 A1, US 2004/096582 A1, US 20040096582 A1, US 20040096582A1, US 2004096582 A1, US 2004096582A1, US-A1-20040096582, US-A1-2004096582, US2004/0096582A1, US2004/096582A1, US20040096582 A1, US20040096582A1, US2004096582 A1, US2004096582A1
InventorsZiyun Wang, Chongying Xu, Ravi Laxman, Thomas Baum, Bryan Hendrix, Jeffrey Roeder
Original AssigneeZiyun Wang, Chongying Xu, Laxman Ravi K., Baum Thomas H., Bryan Hendrix, Jeffrey Roeder
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US 20040096582 A1
Abstract
Silicon precursors for forming silicon-containing films in the manufacture of semiconductor devices, such as low dielectric constant (k) thin films, high k gate silicates, low temperature silicon epitaxial films, and films containing silicon nitride (Si3N4), siliconoxynitride (SiOxNy) and/or silicon dioxide (SiO2). The precursors of the invention are amenable to use in low temperature (e.g., <500° C.) chemical vapor deposition processes, for fabrication of ULSI devices and device structures.
Images(8)
Previous page
Next page
Claims(43)
What is claimed is:
1. A silicon compound selected from the group consisting of:
(A) compounds of the formula:
[SiXn(NR1R2)3-n]2  (1)
 wherein:
R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0≦n≦2;
(B) compounds of the formula (2)
 wherein:
each of R3 can be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
each of R4, R5 and R6 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, C3-C6 cycloalkyl, Si(CH3)3 and SiCl3;
(C) metal source reagent complexes formed by metal cation reaction with deprotonated anionic forms of the compounds (B);
(D) disilicon cycloamides of the formulae (3)-(6):
 wherein:
each of R8 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
each of R9 can be the same as or different from the others and each is independently selected from the group consisting of H and NR8H where R8 is as defined above; and
(E) cyclosilicon compounds of the formula:
wherein:
each of R10 and R11 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
2. A silicon compound of the formula
[SiXn(NR1R2)3-n]2  (1)
 wherein:
R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0≦n≦2.
3. The silicon compound of claim 2, selected from the group consisting of (Et2N)2ClSi—SiCl(NEt2)2, (EtNH)3Si—Si(HNEt)3, (ButNH)2ClSi—SiCl(HNBut)2, (Me2N)2ClSi—SiCl(NMe2)2, Cl2HSi—SiHCl2, and (EtNH)2HSi—SiH(NHEt)2.
4. The silicon compound of claim 2, of the formula:
5. A silicon compound of the formula (2):
wherein:
each of R3 can be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
each of R4, R5 and R6 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, C3-C6 cycloalkyl, Si(CH3)3 and SiCl3.
6. The silicon compound according to claim 5, selected from the group consisting of compounds of the formula:
wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
metal source reagent complexes formed by metal cation reaction with deprotonated anionic forms of the compounds of formula (2a).
7. The silicon compound of claim 6, wherein both R substituents are hydrogen.
8. The silicon compound of claim 6, wherein both R substituents are methyl.
9. The silicon compound of claim 6, of the formula (2a).
10. The silicon compound of claim 6, comprising a metal source reagent complex formed by metal cation reaction with a deprotonated anionic form of a compound of formula (2a).
11. The silicon compound of claim 10, wherein the metal cation comprises a cation of a transition metal.
12. The silicon compound of claim 10, wherein the metal cation comprises a cation of a metal selected from the group consisting of hafnium (Hf), zirconium (Zr), and barium (Ba).
13. A silicon compound selected from the group consisting of disilicon cycloamides of the formulae (3)-(6):
wherein:
each of R8 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl and C3-C6 cycloalkyl; and
each of R9 can be the same as or different from the others and each is independently selected from the group consisting of H and NR8H where R8 is as defined above.
14. A cyclosilicon compound of the formula:
wherein:
each of R10 and R11 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
15. The silicon compound of claim 14, wherein each of R10 and R11 is tertiary butyl (But).
16. (NEt2)2ClSi—SiCl(NEt2)2.
17. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including temperature below 600° C. with a vapor of a silicon compound as in claim 1.
18. The method of claim 17, wherein the silicon compound is of formula (1).
19. The method of claim 18, wherein the silicon-containing film comprises a material selected from the group consisting of silicon oxide, silicon oxynitride and silicon and said temperature is <500° C.
20. The method of claim 19, wherein the silicon-containing compound is selected from the group consisting of (Et2N)2ClSi—SiCl(NEt2)2, (EtNH)3Si—Si(HNEt)3, (ButNH)2ClSi—SiCl(HNBut)2, (Me2N)2ClSi—SiCl(NMe2)2, Cl2HSi—SiHCl2, and (EtNH)2HSi—SiH(NHEt)2.
21. The method of claim 19, wherein the silicon-containing compound comprises a compound of the formula:
22. The method of claim 17, wherein the silicon compound comprises a compound of formula (2).
23. The method of claim 17, wherein the silicon compound is selected from those of the group consisting of compounds of formulae (3)-(6).
24. The method of claim 17, wherein the silicon compound comprises a compound of formula (7).
25. The method of claim 17, wherein said silicon-containing film comprises a film selected from the group consisting of films comprising silicon, silicon nitride (Si3N4), siliconoxynitride (SiOxNy), silicon dioxide (SiO2), low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
26. The method of claim 17, wherein said chemical vapor deposition conditions comprise temperature of from about 400 to about 625° C., pressure of from about 10 to about 100 torr, and the presence of ammonia.
27. The method of claim 17, wherein said chemical vapor deposition conditions comprise temperature of from about 525 to about 625° C., pressure of from about 0.1 to about 10 torr.
28. The method of claim 17, comprising depositing oxynitride deposition of silicon.
29. The method of claim 17, comprising depositing oxynitride deposition of silicate.
31. The method of claim 17, wherein the silicon-containing film comprises silicon nitride.
32. The method of claim 17, wherein said temperature is <500° C.
33. A method of making a compound of the formula:
[SiXn(NR1R2)3-n]2  (1)
wherein:
R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0≦n≦2,
said method comprising reacting a disilane compound of the formula X3Si—SiX3 with an amine (R1R2NH) or lithium amide ((R1R2N)Li compound, wherein X, R1 and R2 are as set out above, according to a reaction selected from the group consisting of the following reactions:
wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
34. A method of forming a metal, metal nitride or metal oxide film on a substrate, comprising contacting said substrate with a precursor metal complex formed by ionic reaction of metal cation with a deprotonated compound formed by deprotonation reaction of a silicon compound of formula (2) as in claim 1.
35. The method of claim 34, wherein said silicon compound has the formula:
wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
36. The method of claim 34, wherein the metal cation comprises cation of a metal selected from the group consisting of hafnium, zirconium and barium.
37. The method of claim 17, wherein the silicon compound comprises a disilicon cycloamide compound.
38. The method of claim 17, wherein the silicon compound comprises a precursor reacted with a co-reactant in a reaction scheme selected from the group consisting of those of reaction scheme (C) below:
wherein A is selected from the group consisting of R3S1—N3, R—N═NR′ and R—N═N+═NR′, wherein each R is independently selected from the group consisting of C1-C3 alkyl and R′ is R or H.
39. The method of claim 38, wherein the silicon compound comprises (NEt2)ClSi—SiCl(NEt2).
40. A method of forming a silicon nitride film on a substrate by chemical vapor deposition, comprising contacting said substrate with vapor of silicon source and nitrogen source compounds, wherein said nitrogen source compounds are other than nitrogen or ammonia, and said chemical vapor deposition is conducted at temperature <550° C., wherein said nitrogen source compound is selected from the group consisting of R-diazo compounds, wherein R is H, C1-C4 alkyl or C3-C6 cycloalkyl, triazoles, tetrazoles, amadines, silylazides, small ring nitrogen compounds, and molecules including organic acyclic or cyclic moieties that contain one or more —N—N bonds.
41. The method of claim 40, wherein said small ring nitrogen compounds are selected from the group consisting of aziridines.
42. A method of forming a silicon epitaxial layer on a substrate at temperature below about 600° C., by contacting the substrate with a silicon precursor in the presence of a substantial excess of a reducing agent.
43. The method of claim 42, wherein said reducing agent comprises an agent selected from the group consisting of hydrogen, silane (SiH4) and disilane (Si2H6).
44. The method of claim 43, wherein the temperature is below about 550° C.
Description
    FIELD OF THE INVENTION
  • [0001]
    The present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such films, e.g., films comprising silicon, silicon nitride (Si3N4), siliconoxynitride (SiOxNy), silicon dioxide (SiO2), etc., low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
  • DESCRIPTION OF THE RELATED ART
  • [0002]
    In semiconductor manufacturing, thin (e.g., <1,000 nanometers thickness) passive layers of chemically inert dielectric materials, such as silicon nitride (Si3N4), siliconoxynitride (SiOxNy) and/or silicon dioxide (SiO2), are widely employed in microelectronic device structures, to function as structural elements of the multi-layered structure, such as sidewall spacer elements, diffusion masks, oxidation barriers, trench isolation coatings, inter-metallic dielectric materials, passivation layers and etch-stop layers.
  • [0003]
    Deposition of silicon-containing films by chemical vapor deposition (CVD) techniques is a highly attractive methodology for forming such films. CVD processes involving low deposition temperatures are particularly desired, e.g., temperatures less than about 550° C., but require the availability and use of suitable precursor compositions for such purpose.
  • [0004]
    Precursors suitable for the formation of dielectric silicon-containing films on semiconductor substrates at low temperatures, e.g., less than about 550° C., must meet the following criteria:
  • [0005]
    (1) be highly volatile, with liquids having boiling points <250° C. at atmospheric pressure being generally preferred, since higher boiling points make delivery of the precursor disproportionately more difficult for the intended application;
  • [0006]
    (2) be thermally stable and less hazardous, relative to silanes, disilane and polysilanes, including silicon source compounds such as trichlorosilane and hexachlorodisilane;
  • [0007]
    (3) have minimum halogen content, to correspondingly minimize formation of particulates and clogging of CVD system pumps by solid byproducts such as quaternary ammonium salts;
  • [0008]
    (4) preferably be free of direct Si—C bonds, to correspondingly minimize carbon contamination of the product films;
  • [0009]
    (5) be free of pyrophoricity as well as any susceptibility to detonation and/or rapid decomposition during storage;
  • [0010]
    (6) preferably have reactive sites consistent with low activation energies in the case of silicon nitride deposition; and
  • [0011]
    (7) have stable organic ligands providing sustained resonance time on the substrate surface to provide high conformality and uniformity of the deposited film, with the organo moiety subsequently being readily liberated, e.g., by a decomposition pathway or co-reaction with another species.
  • [0012]
    As an example of the foregoing considerations, hexachlorodisilane, Cl3Si—SiCl3, might on initial consideration appear to be a suitable candidate precursor for CVD formation of silicon oxide, silicon oxynitride and/or silicon nitride thin film structures, since it possesses a weak silicon-silicon bond, rendering it ostensibly amenable to use at low CVD process temperatures, but such compound is reported to oxidatively decompose to a shock-sensitive material, and shock, long-term storage and/or high temperature handling may result in spontaneous detonation of the compound. Such adverse potential effects therefore cause hexachlorodisilane to be less preferred for use as a silicon-containing film precursor for forming silicon-containing films, e.g., of silicon oxide, silicon oxynitride and/or silicon nitride, on a substrate.
  • [0013]
    Among silicon-containing films, silicon nitride poses particular problems. Silicon nitride deposition at temperatures below 500° C. has attracted particular interest for fabrication of microelectronic device structures, such as diffusion barriers, etch-stop layers and side-wall spacers, with tight geometric characteristics and reduced feature size (<130 nanometers). For the next generation of ultra-large scale integration (ULSI) devices, deposition precursors and processes are desired that accommodate deposition of silicon nitride films at temperatures not exceeding about 450° C. Currently used precursors, e.g., BTBAS or silane/ammonia, typically require temperatures above 600° C. to form high quality Si3N4 films.
  • [0014]
    The art therefore has a continuing need for improved precursors amenable to deposition methods such as chemical vapor deposition, for forming silicon-containing films of the aforementioned types.
  • SUMMARY OF THE INVENTION
  • [0015]
    The present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such silicon-containing films, such as films comprising silicon, silicon nitride (Si3N4), siliconoxynitride (SiOxNy), silicon dioxide (SiO2), etc., silicon-containing low k films, high k gate silicates, and silicon epitaxial films.
  • [0016]
    The present invention in one aspect relates to a silicon compound selected from the group consisting of:
  • [0017]
    (A) compounds of the formula:
  • [SiXn(NR1R2)3-n]2  (1)
  • [0018]
    wherein:
  • [0019]
    R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
  • [0020]
    X is selected from the group consisting of halogen (e.g., bromine, fluorine and chlorine), hydrogen and deuterium; and
  • [0021]
    0≦n≦2;
  • [0022]
    (B) compounds of the formula
  • [0023]
    wherein:
  • [0024]
    each of R3 can be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
  • [0025]
    each of R4, R5 and R6 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, C3-C6 cycloalkyl, Si(CH3)3 and SiCl3;
  • [0026]
    (C) metal source reagent complexes formed by metal cation reaction with deprotonated anionic forms of the compounds (B);
  • [0027]
    (D) disilicon cycloamides of the formulae (3)-(6):
  • [0028]
    wherein:
  • [0029]
    each of R8 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
  • [0030]
    each of R9 can be the same as or different from the others and each is independently selected from the group consisting of H and NR8H where R8 is as defined above; and
  • [0031]
    (E) cyclosilicon compounds of the formula:
  • [0032]
    wherein:
  • [0033]
    each of R10 and R11 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
  • [0034]
    In another aspect, the invention relates to a method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including temperature below 600° C. with a vapor of a silicon compound of a type as described above.
  • [0035]
    Another aspect of the invention relates to a method of making a silicon compound of the formula
  • [SiXn(NR1R2)3-n]2  (1)
  • [0036]
    wherein:
  • [0037]
    R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
  • [0038]
    X is selected from the group consisting of halogen (e.g., bromine, fluorine and chlorine), hydrogen and deuterium; and
  • [0039]
    0≦n≦2,
  • [0040]
    such method comprising reacting a disilane compound of the formula X3Si—SiX3 with an amine (R1R2NH) or lithium amide ((R1R2N)Li compound, wherein X, R1 and R1 are as set out above, according to a reaction selected from the group consisting of the following reactions:
  • [0041]
    A still further aspect of the invention relates to a method of forming a metal, metal nitride or metal oxide film on a substrate, comprising contacting said substrate with a precursor metal complex formed by ionic reaction of metal cation with a deprotonated anionic form of a silicon compound of the formula (2) above, e.g., a compound such as
  • [0042]
    wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
  • [0043]
    Yet another aspect of the invention relates to a method of forming a silicon nitride film on a substrate by chemical vapor deposition, comprising contacting said substrate with vapor of silicon source and nitrogen source compounds, wherein said nitrogen source compounds are other than nitrogen or ammonia, and said chemical vapor deposition is conducted at temperature <550° C., wherein said nitrogen source compound is selected from the group consisting of R-diazo compounds, wherein R is H, C1-C4 alkyl or C3-C6 cycloalkyl, triazoles, tetrazoles, amadines, silylazides, small ring nitrogen compounds, and molecules including organic acyclic or cyclic moieties that contain one or more —N—N bonds.
  • [0044]
    Still another aspect of this invention relates to a method of forming a silicon epitaxial layer on a substrate at low temperature, e.g., a temperature below about 600° C., and preferably below 550° C., by contacting the substrate with a silicon precursor in the presence of a substantial excess of a reducing agent, such as hydrogen, silane (SiH4) or disilane (Si2H6).
  • [0045]
    Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0046]
    [0046]FIG. 1 is an 1H NMR spectrum of (HNEt)3Si—Si(HNEt)3.
  • [0047]
    [0047]FIG. 2 is a 13C NMR spectrum of (HNEt)3Si—Si(HNEt)3.
  • [0048]
    [0048]FIG. 3 is an STA plot for (HNEt)3Si—Si(HNEt)3.
  • [0049]
    [0049]FIG. 4 is an 1H NMR spectrum of (ButNH)2ClSi—SiCl(HNBut)2.
  • [0050]
    [0050]FIG. 5 is a 13C NMR spectrum of (ButNH)2ClSi—SiCl(HNBut)2.
  • [0051]
    [0051]FIG. 6 is an STA plot for (ButNH)2ClSi—SiCl(HNBut)2.
  • [0052]
    [0052]FIG. 7 is an 1H-NMR spectrum of (ButNH)2Si(H)Cl in C6D6.
  • [0053]
    [0053]FIG. 8 is an 1H-NMR spectrum of η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane in C6D6.
  • [0054]
    [0054]FIG. 9 is an STA plot for η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane.
  • [0055]
    [0055]FIG. 10 is a plot of deposition rate as a function of temperature for (HNEt)3Si—Si(HNEt)3 at 10 torr, 10 seem NH3, 10 seem He, and 0.1 ml/minute.
  • [0056]
    [0056]FIG. 11 is a plot of deposition rate as a function of temperature for (NEt2)2ClSi—SiCl(NEt2)2 at 10 torr, 10 sccm NH3, 10 sccm He, and 0.2 ml/minute.
  • [0057]
    [0057]FIG. 12 is a plot of deposition rate as a function of temperature for cyclotrimethylene-bis(t-butylamino)silane at 10 sccm NH3, 10 sccm He, and 0.2 ml/minute.
  • [0058]
    [0058]FIG. 13 is a plot of deposition rate as a function of temperature η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane at 10 torr, 10 sccm NH3, 10 sccm He, and 0.2 ml/minute.
  • DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS THEREOF
  • [0059]
    The present invention relates to silicon precursors for CVD formation of films on substrates, such as silicon precursors for forming low k dielectric films, high k gate silicates, low temperature silicon epitaxial films, and films comprising silicon, silicon oxide, silicon oxynitride, silicon nitride, etc., as well as to corresponding processes for forming such films with such precursors.
  • [0060]
    In one aspect, the invention provides as such precursor a compound of the formula:
  • [SiXn(NR1R2)3-n]2  (1)
  • [0061]
    wherein:
  • [0062]
    R1 and R2 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl;
  • [0063]
    X is selected from the group consisting of halogen (e.g., bromine, fluorine and chlorine), hydrogen and deuterium; and
  • [0064]
    0≦n≦2.
  • [0065]
    One preferred class of compounds of formula (1) has the formula:
  • [0066]
    wherein R1 and R2 are as defined in connection with formula (1).
  • [0067]
    The compounds of formula (1) are usefully employed for forming films on substrates, e.g., by chemical vapor deposition at temperature <500° C. The films that can be formed using such precursor compounds include low dielectric constant (k) thin films, high k gate silicates and silicon epitaxial films. In one aspect of the invention, the films formed using such precursors comprise silicon, silicon oxide, silicon oxynitride and/or silicon nitride.
  • [0068]
    Preferred compounds of formula (1) include (Et2N)2ClSi—SiCl(NEt2)2, (EtNH)3Si—Si(HNEt)3, (ButNH)2ClSi—SiCl(HNBut)2, (Me2N)2ClSi—SiCl(NMe2)2, Cl2HSi—SiHCl2, (EtNH)2HSi—SiH(NHEt)2, and the like.
  • [0069]
    Compounds of formula (1) are readily synthesized by reaction of disilane compounds of the formula X3Si—SiX3 with amine (R1R2NH) or lithium amide ((R1R2N)Li compounds, wherein X, R1 and R2 are as set out above, according to following reactions:
  • [0070]
    as hereinafter more fully described in the examples herein.
  • [0071]
    In specific applications, it may be necessary or desirable to conduct a second reaction to introduce hydrogen in place of the halogen.
  • [0072]
    The invention in another aspect provides a further class of silicon precursor compounds, comprising nitrogen-containing cyclosilicon compounds of the formula:
  • [0073]
    wherein:
  • [0074]
    each of R3 can be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
  • [0075]
    each of R4, R5 and R6 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, C3-C6 cycloalkyl, Si(CH3)3 and SiCl3.
  • [0076]
    A preferred class of compounds of formula (2) includes the compounds of formula (2a):
  • [0077]
    wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl. In one preferred compound of such type, both R substituents are hydrogen. In another preferred compound of such type, both R substituents are methyl.
  • [0078]
    The precursors of formula (2a) contain two silicon atoms in a four-member ring structure with four tertiary butyl (But) groups on the nitrogen atoms. In such compositions, as employed for chemical vapor deposition of silicon nitride, the tertiary butyl groups are effective leaving groups, so that there is minimal But-associated carbon incorporation into films formed from such precursors. In one preferred aspect of the invention, such precursors are usefully employed in low temperature (<500° C.) CVD processes as precursors for silicon nitride films.
  • [0079]
    With reference to the silicon compounds of formula (2a), another class of compounds of the present invention includes those corresponding to formula (2a) but wherein the tertiary butyl (But) groups are replaced by trimethylsilyl (—SiMe3) or trichlorosilyl (—SiCl3) groups.
  • [0080]
    The precursors of formulae (2) and (2a) can be advantageously employed as ligands to form corresponding metal complexes, by deprotonation reaction serving to remove the hydrogen substituents of hydrogen-bearing groups, e.g., the tertiary butyl (But) groups on the nitrogen atoms in formula (2a), to form corresponding anionic species, followed by reaction of the anionic species with metal cations (which can be any metal or transition metal of the Periodic Table, e.g., hafnium (Hf), zirconium (Zr), barium (Ba), etc.) to form corresponding neutral metal source reagent complexes. Such metal source reagent complexes are usefully employed as CVD precursors for metal nitrides, metal oxides and pure metal films.
  • [0081]
    The precursors of formula (2) and their corresponding metal complexes are usefully employed for forming thin films on substrates by chemical vapor deposition.
  • [0082]
    Another class of silicon precursors in accordance with the invention, which are amenable to CVD use at low temperatures, such as in the range of from about 350° C. to about 550° C. for pre and post metal deposition of thin (e.g., 500 Angstroms to 1 micrometer thickness) dielectric films of silicon nitride or silicon dioxide in semiconductor manufacturing, or otherwise for forming silicon nitride or silicon dioxide ceramic thin films as well as films on different substrates, at temperatures in the range of from about 100° C. to about 600° C., comprise the disilicon cycloamides of the formulae (3)-(6):
  • [0083]
    wherein:
  • [0084]
    each of R8 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl; and
  • [0085]
    each of R9 can be the same as or different from the others and each is independently selected from the group consisting of H and NR8H where R8 is as defined above.
  • [0086]
    Another class of compounds useful as silicon precursors in the practice of the invention include those of formula (7):
  • [0087]
    wherein:
  • [0088]
    each of R10 and R11 can be the same as or different from the others and each is independently selected from the group consisting of H, C1-C4 alkyl, and C3-C6 cycloalkyl.
  • [0089]
    One preferred compound of those of formula (7) is the cyclosilicon compound wherein each of R10 and R11 is tertiary butyl (But).
  • [0090]
    The compounds of formulae (1)-(7) can be reacted with suitable co-reactants at relatively low activation energies, as for example in accordance with the reaction scheme (C) shown below:
  • [0091]
    In reaction scheme (C), “Precursors” are any of the precursor compounds of formulae (1)-(7). The co-reactant can be (i) oxygen, ozone or CO2 to form low k dielectric films, (ii) oxygen or a combination of oxygen and nitrogen at deposition temperature <600° C. to form silicon dioxide, (iii) ammonia “or A,” wherein “A” is selected from the group consisting of R3Si—N3, R—N═NR′ and R—N═N+═NR′, each R is independently selected from the group consisting of C1-C3 alkyl substituents, R′ is R or H, and such co-reactant species is employed at deposition temperature <600° C. to form silicon nitride, (iv) dinitrogen oxide (nitrous oxide, N2O), or a mixture of nitrous oxide and ammonia, at temperature <600° C., to form silicon oxynitride, (v) hydrogen and silane, for low temperature silicon epitaxy, and (vi) hafnium and/or zirconium sources, in the presence of oxygen and nitrous oxide, to form silicate gate structures.
  • [0092]
    In accordance with reaction scheme (C), the type of dielectric film produced by the corresponding CVD process can be tailored by choice of the specific co-reactant. For example, hydrogen, ammonia, oxygen or nitrous oxide may be used as alternative single reactants to form the respective silicon nitride, silicon dioxide or silicon oxynitride single component films, or a mixture of two or more of such reactants can be employed in the CVD process with selected one(s) of the formulae (1)-(7) precursors to form corresponding multi-component films, or graded composition films. Other co-reactants may be added to introduce other elemental species (e.g., hafnium, zirconium, barium, titanium, tantalum, etc.).
  • [0093]
    In a further aspect, the invention relates to a method of forming a silicon epitaxial layer on a substrate at temperature below about 600° C., preferably less than about 550° C., by contacting the substrate with a silicon precursor in the presence of a substantial excess of a reducing agent, e.g., a reducing agent such as hydrogen, silane (SiH4), disilane (Si2H6), etc.
  • [0094]
    A further aspect of the invention relates to the use of silicon source compounds with nitrogen source compounds other than nitrogen or ammonia that afford lower activation energy formation of silicon nitride on a substrate, at temperatures <550° C. The use of such alternative co-reactant nitrogen source compounds overcomes the difficulty of depositing silicon nitride at reasonable deposition rates at temperature below 550° C. due to the high activation energy required for nitrogen or ammonia to form Si—N bonds in such low temperature regime.
  • [0095]
    The use of low activation energy co-reactant nitrogen source compounds permits silicon source compounds that would otherwise be unacceptable in use with ammonia or nitrogen, to be efficiently employed to deposit silicon-containing and nitrogen-containing films at temperatures <550° C. Low activation energy co-reactant nitrogen source compounds for such purpose can be of any suitable type, including for example R-diazo compounds, wherein R is H, C1-C4 alkyl or C3-C6 cycloalkyl, triazoles and tetrazoles, amadines, silylazides, small ring nitrogen compounds such as aziridines, or molecules including organic acyclic or cyclic moieties that contain one or more —N—N bonds.
  • [0096]
    In use, co-reactants of the foregoing types are introduced to the CVD reactor as reactive gases, along with the silicon source compound(s). Co-reactant reactive gases of such types, comprising compounds that contain multiple nitrogen atoms, can be used with reactive disilanes such as hexachlorodisilane that would otherwise be wholly unsuitable for formation of silicon nitride films at temperatures <550° C. In such usage, particulate formation is controlled under optimized CVD process conditions to eliminate particle-generating homogenous gas-phase reactions.
  • [0097]
    In application of the co-reactant reaction scheme (C), the silicon-containing precursor is reacted with a desired co-reactant in any suitable manner, e.g., in a single wafer CVD chamber, or in a furnace containing multiple wafers, utilizing process conditions including temperature <550° C. and appertaining pressures, concentrations, flow rates and CVD techniques, as readily determinable within the skill of the art for a given application, based on the disclosure herein.
  • [0098]
    By way of example, in the application of such co-reactant scheme, silicon nitride films can be deposited by deposition techniques such as atomic layer deposition (ALD) involving sequenced pulses wherein the two or more reactants are sequentially introduced to react on the surface bearing the adsorbed reactant species, to form one monolayer of the SiN film at a time.
  • [0099]
    Alternatively, silicon nitride films can be formed by low-pressure CVD techniques, e.g., by a single-wafer deposition process at pressure in a range of from about 1 to about 1000 torr, or in a batch deposition furnace procedure at low pressure such as pressure ≦4 torr, involving chemical reactions that take place in a pressure range of from about 100 mtorr to 4 torr.
  • [0100]
    An illustrative low-pressure chemical vapor deposition (LPCVD) process is described below.
  • [0101]
    In the first step of such illustrative LPCVD process, reactants are introduced into the reaction chamber. Such reactants can be diluted with inert gases, if and as needed, to facilitate reaction control and homogeneous mixing. The reactants are diffused onto the substrate and are adsorbed on the substrate surface.
  • [0102]
    In a second step of the LPCVD process, the reactants adsorbed on the substrate undergo migration and/or chemically react on the surface, with gaseous byproducts of the reaction being desorbed to leave behind the deposited film.
  • [0103]
    The co-reactant deposition may be carried out to form silicon nitride, silicon dioxide or silicon oxynitride films in any suitable reactor, e.g., a vertical flow isothermal LPCVD reactor. A vertical reactor is usefully employed to avoid wafer-to-wafer reactant depletion effects; such reactor does not require temperature ramping, and produces highly uniform deposited films.
  • [0104]
    The vacuum system utilized for providing the low pressure condition of the LPCVD process can be of any suitable type, and can for example include a dry pump or rotary vane pump/roots blower combination and various cold traps if and as needed. Reactor pressure can be controlled by a capacitance manometer feedback to a throttle valve controller.
  • [0105]
    Use of a conventional LPCVD system to carry out reactions of the co-reactant scheme (C), at reactor loadings of eighty 200 or 300 mm diameter silicon wafers at 4-9 mm spacing, produced a uniform conductance around the wafer peripheries by compensating for conductance restrictions attributable to the boats and the sled in such system. The temperature uniformity across the wafer load was ±1° C. as measured by an internal multi-junction thermocouple. Deposition uniformity down the wafer load was improved by employing a temperature ramp. Changing the reactant to precursor ratios from 100:1 to 1:1 optimized deposition conditions. The pressure was typically below 1 torr, being varied from 100 mtorr to 1 torr, and the optimum deposition temperature was in a range of from about 100° C. to about 550° C. In general, the invention may be carried out with delivery of precursors in neat form, via liquid delivery, or bubbler or vaporizer. Solvents can be employed for liquid delivery, such as organic solvents, e.g., amine solvents such as NRxH3-x, wherein R is H or C1-C4 alkyl, etc.
  • [0106]
    As another example of specific precursors useful in the general practice of the invention to form silicon-containing films, such as silicon, silicon oxide, silicon nitride, and silicon oxynitride films, silicate gate materials and low k dielectrics, tetrakisdiethylamidodichlorodisilane, (NEt2)2ClSi—SiCl(NEt2)2 is a precursor containing a silicon-silicon bond with only two chlorines in the molecule, and amido groups which are efficient leaving groups in the formation of silicon-containing films having a low carbon contamination characteristic.
  • [0107]
    Tetrakisdiethylamidodichlorodisilane is readily synthesized as hereinafter more fully described in Example 5 hereof, and is usefully employed to form silicon-containing films of good quality, such as films of silicon, silicon oxide, silicon nitride, silicon oxynitride, etc., by low pressure CVD.
  • [0108]
    The features and advantages of the invention are more fully shown by the following illustrative and non-limiting examples.
  • EXAMPLE 1 Synthesis of (HNEt)3Si—Si(HNEt)3
  • [0109]
    In a 5 L flask, 152 g (0.565 mol) of Cl3SiSiCl3 was added with 4 L of hexanes. The flask was cooled to 0° C. using an ice-bath. EtNH2 (400 g, 8.87 mol; b.p.32° C.) was added to the flask under magnetic stirring. White precipitate material was observed immediately. Upon completion of the addition, the ice-bath was removed and the flask was allowed to warm up to room temperature. The reaction mixture was kept stirring overnight and then refluxed for another two hours. After the reaction mixture was cooled to room temperature, it was filtered through a glass frit filter. The solvent was removed from the filtrate under vacuum. Crude product (152 g) was obtained (84% yield). The pure product ((HNEt)3Si—Si(HNEt)3) was obtained from fractional distillation at about 95° C. under 120 mtorr. Shown in FIGS. 1 and 2 are the 1H— and 13C-NMR spectra respectively. FIG. 3 shows the STA data. 1H NMR (C6D6): δ 0.67 (br, 6H, N-H)1.07 (t, 18H), 2.91 (p, 12H); 13C {1H} NMR (C6D6): δ 0.67 (CH2); C12H36N6Si2 Calcd: C, 44.95; H, 11.32; N, 26.21; Found: C, 44.69; H, 10.75; N, 25.85.
  • [0110]
    The STA data showed the T50 value of (HNEt)3Si—Si(HNEt)3 to be about 185° C., evidencing good volatility and transport properties for chemical vapor deposition.
  • EXAMPLE 2 Synthesis of (ButNH)2ClSi—SiCl(HNBut)2
  • [0111]
    In a 250 mL flask with 180 mL of diethyl ether, 5 g (18.6 mmol) of Cl3SiSiCl3 was added. The flask was cooled to 0° C. in an ice-bath. Under magnetically stirring, ButNH2 (13.6 g/186 mmol) in 30 mL of ether was added into the flask dropwise. White precipitate material was formed immediately. Upon completion of the addition, the ice-bath was removed and the flask was allowed to warm up to room temperature. The reaction mixture was stirred overnight and then refluxed for another two hours. After the reaction mixture was cooled to room temperature, it was filtered through a frit filter. Removal of volatiles from the filtrate gave 6.10 g of white solid crude product in 79% yield. It can further purified by recrystallization from its hexanes-THF mixture solution at 0° C. The crystals have been characterized by X-ray analysis. Shown in FIGS. 4 and 5 are the 1H- and 13C-NMR spectra, respectively. FIG. 6 shows the STA data for the product, (ButNH)2ClSi—SiCl(HNBut)2, which had a T50 value of about 196° C., evidencing good volatility and transport properties for chemical vapor deposition.
  • [0112]
    [0112]1H NMR (C6D6): δ 1.28 (s, 36H), 1.59 (br, 4H, N—H), 13C {1H} NMR (C6D6): δ 33.4 (CH3), 50.8 (C); C16H40Cl2N4Si2 Calcd: C, 46.24; H, 9.70; N, 13.48; Found: C, 45.98; H, 9.99; N, 13.14.
  • EXAMPLE 3 Synthesis of (ButNH)2Si(H)Cl
  • [0113]
    The general reactions were carried out under a steady flow of nitrogen. A 500 mL Schlenk flask equipped a magnetic stirring bar, was charged with 250 mL of dry ether and 21.6 g of tBuNH2 and. To this flask, 10 g, 73.8 mmol of HSiCl3 in 50 mL of ether was added dropwise at 0° C. Upon completion of the addition, the mixture was stirred overnight. The mixture was then refluxed for an additional 4 hours. It was cooled to room temperature and filtered through Celite®. Solvents were removal of by quick distillation or vacuum. The crude yield was 80%. It was then purified by fractional vacuum distillation to around 98% in purity. The product, (ButNH)2Si(H)Cl, was characterized by solution NMR in C6D6 (FIG. 7). 1H NMR (C6D6), δ (ppm), 5.48 (t, 1H), 1.09 (s, 18H).
  • EXAMPLE 4 Synthesis of η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane
  • [0114]
    The general reactions were carried out under a steady flow of nitrogen using Schlenk techniques. A 250 mL Schlenk flask was charged with 9.22 g, 44.2 mmol of di(tert-butylamino)(chloro)silane in 150 mL of hexanes and a stir bar. Then 26 mL of 1.7 M tert-butyllithium solution in patane was added into the Schlenk flask slowly at 0° C., under magnetic stirring. A white precipitate of LiCl formed during the addition. Upon completion of the addition, the mixture was refluxed overnight. The reaction mixture was then allowed to cool and filtered through Celite® to obtain a slightly yellow clear solution. All volatiles were removed under vacuum and the crude yield was about 60%. This crude product was purified by vacuum column distillation. The pure product was received while the oil bath temperature was set to 170° C. and the vacuum at 200 mtorr. It was characterized by solution NMR in C6D6 (FIG. 8) and STA (FIG. 9). 1H-NMR (C6D6), δ (ppm), 5.31 (dd, 2H, cis or trans isomer), 5.12 (d, 2H, cis or trans isomers), 1.42 (s, 18H, cis or trans isomer), 1.41 (s, 18H, cis or trans isomer) and 1.24 (s, 18H, both isomers).
  • EXAMPLE 5 Synthesis of (NEt2)2ClSiSiCl(NEt2)2
  • [0115]
    In a 250 mL flask with 180 mL of ether, 5 g, 18.6 mmol of Cl3SiSiCl3 was added. The flask was cooled to 0° C. using an ice-bath. While kept stirring, Et2NH2, 16.3 g, 223 mmol in 30 mL of ether was added dropwise into the flask. Upon completion of addition, the ice-bath was removed and the flask was allowed to warm up to room temperature. The reaction mixture was kept stirring overnight and then refluxed for another two hours. After the reaction mixture was cooled to room temperature, it was filtered through a frit filter. The solvent was removed from the filtrate by vacuum. The product tetrakisdiethylamidodichlorodisilane was obtained from column distillation while controlling the oil bath temperature at around 165° C. 6.35 g, 15.2 mmol product, (NEt2)2ClSiSiCl(NEt2)2, was obtained which corresponded to 82% yield. 1H NMR in C6D6: 1.05 (t, 16H), 3.02 (q, 24H). C16H40Cl2N4Si2 Calcd: C, 46.24; H, 9.70; N, 13.48; Found: C, 46.17; H, 9.73; N, 13.33.
  • EXAMPLE 6 Silicon Nitride Deposition From (HNEt)3Si—Si(HNEt)3
  • [0116]
    A solution of the compound of Example 1, (HNEt)3Si—Si(HNEt)3, was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.1 ml/minute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 10 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 10 torr during deposition. The growth rate of the silicon nitride films decreased from 470 Å/minute at a wafer temperature of 625° C. to 26 Å/minute at 450° C. as shown in FIG. 10.
  • [0117]
    Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), revealed that higher pressures and higher NH3 flows increased the N/Si ratio to the stoichiometric value of 1.33 and decreased the impurity carbon content as shown in Table 1 below.
    TABLE 1
    Film composition for various deposition conditions using the precursor
    (HNEt)3Si—Si(HNEt)3.
    Rate
    NH3 T P (Å/ H C O
    (sccm) (° C.) (torr) min) n (at %) (at %) (at %) N/Si
    10 550 10 196 1.87 20.5 13.5 13.3 1.15
    100 530 40 72 1.78 25.5 5.2 11.2 1.31
    100 530 80 59 1.79 21.5 5 5.9 1.37
    140 624 80 184 1.84 14.5 3.6 0.9 1.36
  • EXAMPLE 7 Silicon Nitride Deposition with a Pulsed Process From (HNEt)3Si—Si(HNEt)3
  • [0118]
    (HNEt)3Si—Si(HNEt)3 was vaporized continuously at a rate of 100 μmol/minute at 120° C. with 10 sccm of He carrier gas and directed either to the deposition process or to a process bypass. NH3 was supplied continuously to the process at 10 sccm.
  • [0119]
    During the periods when precursor was directed to the process, the NH3 was activated only by the temperature of the wafer surface. An increased transmissive optical frequency range was observed, indicating a higher band gap, when the precursor supply time to the wafer was decreased relative to the precursor supply time to the bypass. Alternatively, during the periods where the precursor was directed to the bypass, a hot filament network above the wafer surface was heated to supplement the activation of the NH3. The filament either was made of tungsten and held at 2000K or it was made of Pt and held at 600° C.
  • [0120]
    The period of time during which the precursor was directed at the process was enough to deposit at least a few monolayers. The period of time during which the precursor was directed to bypass was enough to increase the N:Si ratio to above 1.3. The NH3 supply was constantly directed to the chamber, or diverted to bypass when the precursor was supplied to the wafer surface. Additionally, during the time when the precursor was directed to bypass, the chamber pressure was able to be increased to substantially higher than the deposition pressure (e.g., 100 Torr). The precursor and pulsed nitrogen source were also able to be separated temporally.
  • EXAMPLE 8 Silicon Nitride Deposition From (NEt2)2ClSi—SiCl(NEt2)2
  • [0121]
    A solution of the compound of Example 5, (NEt2)2ClSi—SiCl(NEt2)2, was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.2 ml/minute into a vaporizer that was maintained at temperature of 120° C. and had a flow of 10 sccm of He as a carrier gas. The vapor was mixed with 10 sccm of NH3 in a showerhead vapor disperser device that was held at temperature of 120° C., and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at pressure of 10 torr during deposition. The growth rate of the silicon nitride films decreased from 650 Å/minute at a wafer temperature of 625° C. to 9 Å/minute at 450° C., as shown in FIG. 11. (The index of refraction, n, was >2.2 in all cases, and some films contained Cl.)
  • EXAMPLE 9 Silicon Nitride Deposition From Cyclotrimethylene-bis(t-butylamino)silane
  • [0122]
    A solution of the compound cyclotrimethylene-bis(t-butylamino)silane was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.2 ml/minute into a vaporizer that was maintained at temperature of 120° C. and had a flow of 10 sccm of He as a carrier gas. The vapor was mixed with 10 sccm of NH3 in a showerhead vapor disperser that was held at temperature of 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 2, 5, or 10 torr during deposition. The growth rate of the silicon nitride films decreased from 53 Å/minute at a wafer temperature of 625° C. to 9 Å/minute at 575° C. as shown in FIG. 12. There was no measurable effect of pressure on the growth rate, however, which increased from 1.65 to 1.73 as the pressure decreased from 10 torr to 2 torr at 575° C.
  • EXAMPLE 10 Silicon Nitride Deposition From η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane
  • [0123]
    A solution of the compound of Example 4, η-(N,N-t-butyl)-di(t-butylamino)cyclodisilane, was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.2 ml/minute into a vaporizer that was held at 120° C. and had a flow of 10 sccm of He as a carrier gas. The vapor was mixed with 10 sccm of NH3 in a showerhead vapor disperser that was held at 120° C. and the vapor was thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 10 torr during deposition. The growth rate of the silicon nitride films decreased from 15 Å/minute at a wafer temperature of 625° C. to 2 Å/minute at 575° C. as shown FIG. 13.
  • [0124]
    While the invention has been described herein with reference to various specific embodiments, it will be appreciated that the invention is not thus limited, and extends to and encompasses various other modifications and embodiments, as will be appreciated by those ordinarily skilled in the art. Accordingly, the invention is intended to be broadly construed and interpreted, in accordance with the ensuing claims.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US5578530 *Jul 12, 1995Nov 26, 1996Sony CorporationManufacturing method of semiconductor device which includes forming a silicon nitride layer using a Si, N, and F containing compound
US6013235 *Jul 19, 1999Jan 11, 2000Dow Corning CorporationConversion of direct process high-boiling residue to monosilanes
US6383955 *Jun 7, 1999May 7, 2002Asm Japan K.K.Silicone polymer insulation film on semiconductor substrate and method for forming the film
US6410463 *Oct 18, 2000Jun 25, 2002Asm Japan K.K.Method for forming film with low dielectric constant on semiconductor substrate
US6936548 *Nov 27, 2002Aug 30, 2005L'air Liquide, Societe Anonyme Pour L'etude Et, L'exploitation Des Procedes Georges ClaudeMethod for depositing silicon nitride films and silicon oxynitride films by chemical vapor deposition
US7019159 *Nov 27, 2002Mar 28, 2006L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges ClaudeHexakis(monohydrocarbylamino) disilanes and method for the preparation thereof
US7064083 *Sep 8, 2005Jun 20, 2006L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges ClaudeHexakis(monohydrocarbylamino)disilanes and method for the preparation thereof
US7132723 *Nov 14, 2002Nov 7, 2006Raytheon CompanyMicro electro-mechanical system device with piezoelectric thin film actuator
US20040138489 *Oct 31, 2003Jul 15, 2004Ziyun WangComposition and method for low temperature deposition of silicon-containing films
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6943126 *Dec 6, 2002Sep 13, 2005Cypress Semiconductor CorporationDeuterium incorporated nitride
US6992019 *Jun 12, 2003Jan 31, 2006Samsung Electronics Co., Ltd.Methods for forming silicon dioxide layers on substrates using atomic layer deposition
US7077904Apr 23, 2003Jul 18, 2006Samsung Electronics Co., Ltd.Method for atomic layer deposition (ALD) of silicon oxide film
US7084076Feb 19, 2004Aug 1, 2006Samsung Electronics, Co., Ltd.Method for forming silicon dioxide film using siloxane
US7115166Apr 21, 2004Oct 3, 2006Micron Technology, Inc.Systems and methods for forming strontium- and/or barium-containing layers
US7115528 *Apr 29, 2003Oct 3, 2006Micron Technology, Inc.Systems and method for forming silicon oxide layers
US7122464Aug 30, 2004Oct 17, 2006Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US7196007Aug 30, 2004Mar 27, 2007Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US7294582Aug 25, 2005Nov 13, 2007Asm International, N.V.Low temperature silicon compound deposition
US7297641Jul 18, 2003Nov 20, 2007Asm America, Inc.Method to form ultra high quality silicon-containing compound layers
US7300870Aug 29, 2005Nov 27, 2007Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using organic amines
US7332032Sep 1, 2004Feb 19, 2008Micron Technology, Inc.Precursor mixtures for use in preparing layers on substrates
US7332442Jul 12, 2006Feb 19, 2008Micron Technology, Inc.Systems and methods for forming metal oxide layers
US7482284Feb 28, 2007Jan 27, 2009Micron Technology, Inc.Deposition methods for forming silicon oxide layers
US7544615Nov 21, 2007Jun 9, 2009Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using organic amines
US7560393Feb 28, 2007Jul 14, 2009Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US7629267Dec 8, 2009Asm International N.V.High stress nitride film and method for formation thereof
US7651953Jan 26, 2010Asm America, Inc.Method to form ultra high quality silicon-containing compound layers
US7678708Mar 16, 2010Micron Technology, Inc.Systems and methods for forming metal oxide layers
US7691757Jun 21, 2007Apr 6, 2010Asm International N.V.Deposition of complex nitride films
US7713346Oct 7, 2008May 11, 2010Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films
US7718518Dec 14, 2006May 18, 2010Asm International N.V.Low temperature doped silicon layer formation
US7732350Dec 4, 2006Jun 8, 2010Asm International N.V.Chemical vapor deposition of TiN films in a batch reactor
US7740822 *Mar 17, 2006Jun 22, 2010Toagosei Co., Ltd.Method for purification of disilicon hexachloride and high purity disilicon hexachloride
US7781605Aug 24, 2010Advanced Technology Materials, Inc.Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US7786320Aug 31, 2010Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7803719Feb 24, 2006Sep 28, 2010Freescale Semiconductor, Inc.Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device
US7833906Nov 16, 2010Asm International N.V.Titanium silicon nitride deposition
US7863203Jan 24, 2008Jan 4, 2011Advanced Technology Materials, Inc.Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US7910765Mar 22, 2011Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7943501Jan 3, 2008May 17, 2011Micron Technology, Inc.Systems and methods of forming tantalum silicide layers
US7964513Jun 21, 2011Asm America, Inc.Method to form ultra high quality silicon-containing compound layers
US7966969Jun 28, 2011Asm International N.V.Deposition of TiN films in a batch reactor
US7972663 *Jul 5, 2011Applied Materials, Inc.Method and apparatus for forming a high quality low temperature silicon nitride layer
US8114219Feb 26, 2010Feb 14, 2012Micron Technology, Inc.Systems and methods for forming metal oxide layers
US8242032Aug 14, 2012Advanced Technology Materials, Inc.Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US8367854Feb 11, 2010Feb 5, 2013Wacker Chemie AgMethod for producing and stabilizing oligoaminosilanes
US8377511 *Apr 3, 2006Feb 19, 2013L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges ClaudeMethod for depositing silicon nitride films and/or silicon oxynitride films by chemical vapor deposition
US8394725Mar 12, 2013Micron Technology, Inc.Systems and methods for forming metal oxide layers
US8617312Sep 14, 2006Dec 31, 2013Micron Technology, Inc.Systems and methods for forming layers that contain niobium and/or tantalum
US8772524 *Aug 11, 2009Jul 8, 2014Dow Corning CorporationCVD precursors
US9102693Jul 17, 2014Aug 11, 2015Entegris, Inc.Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US9117664 *May 19, 2014Aug 25, 2015Dow Corning CorporationCVD precursors
US9337018May 24, 2013May 10, 2016Air Products And Chemicals, Inc.Methods for depositing films with organoaminodisilane precursors
US9337054Jun 27, 2008May 10, 2016Entegris, Inc.Precursors for silicon dioxide gap fill
US9443736 *May 22, 2013Sep 13, 2016Entegris, Inc.Silylene compositions and methods of use thereof
US20030203113 *Apr 23, 2003Oct 30, 2003Cho Byoung HaMethod for atomic layer deposition (ALD) of silicon oxide film
US20040018694 *Jun 12, 2003Jan 29, 2004Samsung Electronics Co., Ltd.Methods for forming silicon dioxide layers on substrates using atomic layer deposition
US20040180557 *Feb 19, 2004Sep 16, 2004Samsung Electronics Co., Ltd.Method for forming silicon dioxide film using siloxane
US20040194706 *Dec 19, 2003Oct 7, 2004Shulin WangMethod and apparatus for forming a high quality low temperature silicon nitride layer
US20040197946 *Apr 21, 2004Oct 7, 2004Micron Technology, Inc.Systems and methods for forming strontium-and/or barium-containing layers
US20040219746 *Apr 29, 2003Nov 4, 2004Micron Technology, Inc.Systems and methods for forming metal oxide layers
US20050028733 *Aug 30, 2004Feb 10, 2005Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US20050032360 *Aug 30, 2004Feb 10, 2005Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US20050118837 *Jul 18, 2003Jun 2, 2005Todd Michael A.Method to form ultra high quality silicon-containing compound layers
US20050227017 *Oct 28, 2004Oct 13, 2005Yoshihide SenzakiLow temperature deposition of silicon nitride
US20050287804 *Aug 29, 2005Dec 29, 2005Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using organic amines
US20060040510 *Sep 14, 2005Feb 23, 2006Joo-Won LeeSemiconductor device with silicon dioxide layers formed using atomic layer deposition
US20060048711 *Sep 1, 2005Mar 9, 2006Micron Technology, Inc.Systems and methods of forming tantalum silicide layers
US20060060137 *Mar 31, 2005Mar 23, 2006Albert HasperDeposition of TiN films in a batch reactor
US20060062913 *Sep 17, 2004Mar 23, 2006Yun-Ren WangProcess for depositing btbas-based silicon nitride films
US20060088985 *Aug 25, 2005Apr 27, 2006Ruben HaverkortLow temperature silicon compound deposition
US20060090694 *Dec 16, 2005May 4, 2006Moohan Co., Ltd.Method for atomic layer deposition (ALD) of silicon oxide film
US20060199357 *Mar 6, 2006Sep 7, 2006Wan Yuet MHigh stress nitride film and method for formation thereof
US20060252244 *Jul 12, 2006Nov 9, 2006Micron Technology, Inc.Systems and methods for forming metal oxide layers
US20060292788 *Aug 31, 2006Dec 28, 2006Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US20070006798 *Sep 14, 2006Jan 11, 2007Micron Technology, Inc.Systems and methods for forming strontium-and/or barium-containing layers
US20070077775 *Dec 4, 2006Apr 5, 2007Albert HasperDeposition of TiN films in a batch reactor
US20070141812 *Dec 14, 2006Jun 21, 2007Zagwijn Peter MLow temperature doped silicon layer formation
US20070155190 *Feb 28, 2007Jul 5, 2007Micron Technology, Inc.Systems and methods for forming metal oxide layers
US20070166999 *Feb 28, 2007Jul 19, 2007Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using disilazanes
US20080038936 *Oct 23, 2007Feb 14, 2008Asm America, Inc.Method to form ultra high quality silicon-containing compound layers
US20080064210 *Nov 21, 2007Mar 13, 2008Micron Technology, Inc.Systems and methods of forming refractory metal nitride layers using organic amines
US20080102629 *Jan 3, 2008May 1, 2008Micron Technology, Inc.Systems and methods of forming tantalum silicide layers
US20080160174 *Jan 24, 2008Jul 3, 2008Advanced Technology Materials, Inc.Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US20080207005 *Feb 2, 2005Aug 28, 2008Freescale Semiconductor, Inc.Wafer Cleaning After Via-Etching
US20080210157 *Sep 14, 2006Sep 4, 2008Micron Technology, Inc.Systems and methods for forming strontium-and/or barium-containing layers
US20090045164 *Feb 3, 2006Feb 19, 2009Freescale Semiconductor, Inc."universal" barrier cmp slurry for use with low dielectric constant interlayer dielectrics
US20090053124 *Mar 17, 2006Feb 26, 2009Toagosei Co., Ltd.Method for purification of disilicon hexachloride and high purity disilicon hexachloride
US20090084288 *Oct 7, 2008Apr 2, 2009Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films
US20090115031 *Feb 24, 2006May 7, 2009Freescale Semiconductor, Inc.Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device
US20090149033 *Jan 13, 2009Jun 11, 2009Micron Technology, Inc.Systems and methods for forming metal oxide layers
US20090281344 *Nov 12, 2009Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US20090301867 *Feb 24, 2006Dec 10, 2009Citibank N.A.Integrated system for semiconductor substrate processing using liquid phase metal deposition
US20090311857 *Aug 24, 2009Dec 17, 2009Asm America, Inc.Method to form ultra high quality silicon-containing compound layers
US20100029094 *Oct 13, 2009Feb 4, 2010Applied Materials, Inc.Method and Apparatus for Forming a High Quality Low Temperature Silicon Nitride Layer
US20100068894 *Oct 13, 2009Mar 18, 2010Advanced Technology Materials, Inc.Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20100112211 *Apr 13, 2008May 6, 2010Advanced Technology Materials, Inc.Zirconium, hafnium, titanium, and silicon precursors for ald/cvd
US20100164057 *Jun 27, 2008Jul 1, 2010Advanced Technology Materials, Inc.Precursors for silicon dioxide gap fill
US20100221428 *Apr 3, 2006Sep 2, 2010Christian DussarratMethod for depositing silicon nitride films and/or silicon oxynitride films by chemical vapor deposition
US20100285663 *Jul 17, 2010Nov 11, 2010Advanced Technology Materials, Inc.Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US20110165762 *Jan 4, 2011Jul 7, 2011Advanced Technology Materials, Inc.Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US20110195582 *Aug 11, 2009Aug 11, 2011Xiaobing ZhouCVD Precursors
US20140256159 *May 19, 2014Sep 11, 2014Dow Corning CorporationCvd precursors
US20150147824 *May 22, 2013May 28, 2015Advanced Technology Materials, Inc.Silicon precursors for low temperature ald of silicon-based thin-films
US20150147871 *Jun 2, 2014May 28, 2015Air Products And Chemicals, Inc.Aza-polysilane precursors and methods for depositing films comprising same
CN102307883A *Feb 11, 2010Jan 4, 2012瓦克化学股份公司Method for producing and stabilizing oligoaminosilanes
CN102307883BFeb 11, 2010Jul 16, 2014瓦克化学股份公司Method for producing and stabilizing oligoaminosilanes
CN103814035A *Aug 31, 2012May 21, 2014新日铁住金化学株式会社Organic electroluminescent element material having silicon-containing four membered ring structure, and organic electroluminescent element
WO2007025565A1 *Sep 1, 2005Mar 8, 2007Freescale Semiconductor, Inc.Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device
WO2010094610A1 *Feb 11, 2010Aug 26, 2010Wacker Chemie AgMethod for producing and stabilizing oligoaminosilanes
Classifications
U.S. Classification427/255.27, 257/E21.279, 257/E21.268, 257/E21.293, 556/412
International ClassificationC07F7/10, H01L21/318, C23C16/34, C30B29/06, C23C16/40, H01L21/314, C07F7/12, C07F7/02, H01L21/316, C23C16/30, C30B25/02
Cooperative ClassificationC30B29/06, H01L21/02219, H01L21/0228, H01L21/0217, C07F7/025, H01L21/3185, C23C16/345, H01L21/02271, C07F7/10, C07F7/12, C23C16/402, C23C16/308, C30B25/02, H01L21/02222, H01L21/3144, H01L21/31612
European ClassificationH01L21/02K2E3B6F, H01L21/02K2C1L9, H01L21/02K2E3B6, H01L21/02K2C7C6B, H01L21/02K2C7C6, H01L21/314B1, C23C16/34C, C07F7/10, C23C16/40B2, C30B29/06, C30B25/02, H01L21/316B2B, H01L21/318B, C07F7/12, C23C16/30E, C07F7/02B
Legal Events
DateCodeEventDescription
Jan 21, 2003ASAssignment
Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WANG, ZIYUN;XU, CHONGYING;LAXMAN, RAVI K;AND OTHERS;REEL/FRAME:013687/0327;SIGNING DATES FROM 20021114 TO 20021212
Sep 28, 2012FPAYFee payment
Year of fee payment: 4
May 1, 2014ASAssignment
Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y
Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032815/0852
Effective date: 20140430
May 2, 2014ASAssignment
Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y
Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032812/0192
Effective date: 20140430
Feb 4, 2015ASAssignment
Owner name: ENTEGRIS, INC., MASSACHUSETTS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ADVANCED TECHNOLOGY MATERIALS, INC.;REEL/FRAME:034894/0025
Effective date: 20150204